Protective self-aligned buffer layers for damascene interconnects

ABSTRACT

Protective self aligned buffer (PSAB) layers are layers of material that are selectively formed at the surface of metal layers in a partially fabricated semiconductor device. In a Damascene interconnect, PSAB layer typically resides at an interface between the metal layer and a dielectric diffusion barrier layer. PSAB layers promote improved adhesion between a metal layer and an adjacent dielectric diffusion barrier layer. Further, PSAB layers can protect metal surfaces from inadvertent oxidation during fabrication process. A PSAB layer may be formed entirely within the top portion of a metal layer, by, for example, chemically converting metal surface to a thin layer of metal silicide. Thickness of PSAB layers, and, consequently resistance of interconnects can be controlled by partially passivating metal surface prior to formation of PSAB layer. Such passivation can be accomplished by controllably treating metal surface with a nitrogen-containing compound to convert metal to metal nitride.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part claiming priority under 35USC 120 from U.S. patent application Ser. No. 10/980,076 filed Nov. 3,2004, now U.S. Pat. No. 7,396,759 titled “Protection of Cu DamasceneInterconnects by Formation of a Self-aligned Buffer Layer,” naming vanSchravendijk et al. as inventors, which is incorporated herein byreference in its entirety for all purposes.

FIELD OF THE INVENTION

The present invention pertains to methods of forming layers of materialon a partially fabricated integrated circuit. Specifically, theinvention pertains to methods for forming protective self-aligned buffer(PSAB) layers for use in Damascene interconnects.

BACKGROUND OF THE INVENTION

Damascene processing is a method for forming metal lines on integratedcircuits. It involves formation of inlaid metal lines in trenches andvias formed in a dielectric layer (inter metal dielectric). Damasceneprocessing is often a preferred method because it requires fewerprocessing steps than other methods and offers a higher yield. It isalso particularly well-suited to metals such as copper that cannot bereadily patterned by plasma etching.

In a typical Damascene process flow, metal is deposited onto a patterneddielectric to fill the vias and trenches formed in the dielectric layer.The resulting metallization layer is typically formed either directly ona layer carrying active devices, or on a lower lying metallizationlayer. A thin layer of a dielectric diffusion barrier material, such assilicon carbide or silicon nitride, is deposited between adjacentmetallization layers to prevent diffusion of metal into bulk layers ofdielectric. In a typical integrated circuit (IC), several metallizationlayers are deposited on top of each other forming a stack, in whichmetal-filled vias and trenches serve as IC conducting paths. Theconducting paths of one metallization layer are connected to theconducting paths of an underlying or overlying layer by a series ofDamascene interconnects.

Fabrication of these interconnects presents several challenges, whichbecome more and more significant as the dimensions of IC device featurescontinue to shrink. Currently, at the 90 nm technology node and at moreadvanced nodes, there is a strong need for interconnect fabricationmethods that can provide interconnects with improved lifetime andreliability.

SUMMARY OF THE INVENTION

To address these needs, IC devices having interconnects with protectiveself aligned buffer (PSAB) layers are provided. Methods of forming PSABlayers during IC device fabrication are also described herein. PSABlayers are layers of material that are selectively formed at the surfaceof metal layers of a partially fabricated semiconductor device. PSABlayers may be capable of improving several properties of Damasceneinterconnects. For example, a PSAB layer may promote improved adhesionbetween a metal layer and an adjacent dielectric diffusion barrierlayer. Further, PSAB layers can protect metal surfaces from inadvertentoxidation during fabrication processes and can lead to a decrease inmetal electromigration during end use of a semiconductor device. Methodsof forming PSAB-containing interconnects having reduced stress migrationparameters are also provided.

In some embodiments, a PSAB layer is formed entirely within the topportion of a metal layer, such that it is substantially at the samelevel as the plane of a dielectric field region adjacent to the metallayer. This can be accomplished by chemically transforming exposed metalatoms to a desired material. For example, Cu can react with SiH₄ to forma thin PSAB layer of Cu_(x)Si_(y) within the top portion of metal layer.While PSAB layers generally increase resistance of interconnects, suchresistance shift can be efficiently controlled. Specifically, thicknessof PSAB layers, and, consequently, resistance of an interconnect can becontrolled by partially passivating exposed metal surfaces, prior toformation of the PSAB layer. Such passivation can be accomplished by,for example, controllably reacting surface atoms with anitrogen-containing compound (e.g., NH₃) to form a metal nitride. Suchpassivation depletes the amount of metal atoms (in a zero oxidationstate) that are available for reaction to form the PSAB layer, and,consequently, controls the thickness of the PSAB layer and resistance ofan interconnect.

Further, in some embodiments, resistance of interconnects is controlledby a “pinning” operation which serves to limit the diffusion ofnon-conductive species into the metal line. In some embodiments,“pinning” comprises chemically transforming the first-formed PSAB layeras well as transforming intermediates and by-products of a first PSABforming reaction to form a thin layer of dielectric material, such asSi_(x)N_(y) or Si_(x)C_(y), at the interface between the metal layer anda layer of dielectric diffusion barrier material. Such layer is referredto as a “pinned PSAB layer”. This dielectric material may or may nothave Cu dissolved within it and therefore in some embodiments could havesmall amount of conductivity. In some embodiments, pinned PSAB layerincludes some unmodified material of the first PSAB layer, Such asCu_(x)Si_(y), Cu_(x)Ge_(y), etc.

In some embodiments, PSAB layers have a graded composition, withconcentration of PSAB material gradually decreasing as the distance fromthe interface with the diffusion barrier increases. Thus, according tosome embodiments, PSAB layers may be viewed as layers of metalimpregnated with a PSAB material (e.g., Cu_(x)Si_(y), and/orSi_(x)N_(y)) at an interface with a dielectric diffusion barrier, whereconcentration of the PSAB material is gradually changing.

In one aspect, a method of forming a protective layer of material on orwithin an exposed metal surface of a partially fabricated semiconductordevice is provided. For example, the method can be practiced on asubstrate having a metal layer comprising a metal fill located in aDamascene region of the partially fabricated device. The substrate, insome embodiments, is received after a chemical mechanical polishing(CMP) operation and has a planarized surface. In a first operation ofone embodiment of the provided method, the substrate having a pattern ofmetal layers in a layer of dielectric is contacted with a passivatingreagent to partially passivate the metal surface. In one embodiment, anitrogen containing reagent, e.g., NH₃, contacts the partiallyfabricated device and interacts with an exposed metal surface to form ametal nitride, e.g., Cu_(x)N_(y), at the surface of the metal layer,thereby passivating metal surface to a subsequent PSAB-forming reaction.Other nitrogen containing compounds that may be used include N₂H₄, andamines. Preferably such compounds are capable of passivating the surfaceof the metal in the absence of plasma. Typically plasma is not usedduring passivation with NH₃, for example. After the metal surface hasbeen partially passivated, the substrate is contacted with a secondreactant, such that the second reactant reacts with unpassivated metalatoms of the metal layer and chemically transforms the top portion ofthe metal layer into a first PSAB layer. In some embodiments, the secondreactant comprises a second reactant gas or vapor selected from thegroup consisting of SiH₄, GeH₄, PH₃, B₂H₆, AsH₃, CH₄, C_(x)H_(y), H₂S,H₂Se, and H₂Te. The first PSAB layer may include, in certainembodiments, material selected from the group consisting ofCu_(x)Si_(y), Cu_(x)Ge_(y), Cu_(x)P_(y), Cu_(x)B_(y), Cu_(x)As_(y),Cu_(x)C_(y), Cu_(x)S_(y), Cu_(x)Se_(y), and Cu_(x)Te_(y). Plasma istypically not used during this operation.

In some embodiments, the first PSAB layer resides entirely within themetal layer. The depth of the first PSAB layer is regulated by an amountof the passivated material (e.g., metal nitride) formed in the firstoperation, and can range, for example, between 10-1000 Å. The greaterthe amount of the passivated material formed at the metal surface, theless is the depth of the first PSAB layer. Thus, the thickness of thefirst PSAB layer, and, consequently, resistance of interconnect, iscontrolled via a partial passivation of exposed metal surface. Incertain embodiments, PSAB layers having a thickness ranging betweenabout 10-60 Å can be formed in a controlled fashion. Control can beachieved, in some embodiments, by regulating the contact time of thenitrogen containing passivating reagent with the substrate.

In some embodiments, the nitrogen containing passivating reagentselectively transforms exposed portions of the metal layer, withouttransforming other exposed materials of the semiconductor substrate,e.g., a dielectric layer.

Passivation and formation of the first PSAB layer can be performed in avariety of types of apparatus. For example, different types of CVDapparatus may be employed. In some embodiments, both operations areperformed in the same apparatus, e.g., in a plasma enhanced chemicalvapor deposition (PECVD) apparatus. In some embodiments, a multi-stationapparatus is used to implement described methods. It is also possible toperform the PSAB process in an apparatus having multiple chambers.

In some embodiments, passivation and formation of a first PSAB layer iscarried out in a PECVD apparatus, but plasma is not used during thesetwo operations. Plasma is used, in some embodiments, during a pre-cleanoperation, which in some implementations of the method is performedprior to passivation of the metal surface. Pre-clean is typicallyperformed using reducing gases, such as H₂ and NH₃ in a plasma, whichmay be generated in some embodiments using high frequency (HF) and lowfrequency (LF) radio frequency (RF) power sources. Pre-cleaning removescontaminants and metal oxide from the surface of the substrate andprovides a clean metal surface for PSAB formation.

The pre-cleaning, passivation, and formation of the first PSAB layer canbe carried out in one apparatus, without exposing the substrate toambient atmosphere containing moisture and oxygen.

In some embodiments, passivation and formation of the first PSAB layeris carried out at a temperature range from about 20° C. to about 500°C., at a pressure range of about 10 mTorr-100 Torr, and using flow ratesfor a nitrogen-containing reactant and for the second reactant (e.g.,SiH₄) of about 10 mTorr-100 Torr. In some embodiments, contact times ofa nitrogen containing reagent and of a second reactant (e.g., SiH₄) witha substrate are within the range of 0.5-5000 seconds.

In some embodiments, the first formed PSAB layer may be further treatedto form a so-called “pinned” PSAB layer. “Pinning” is often used tochemically transform intermediates and by-products generated duringformation of the first PSAB layer to materials that do not readilydiffuse into the depth of metal lines. Thus, pinning, controlsinterconnect resistance by limiting diffusion of non-conducting speciesinto metal-filled vias and trenches. In some embodiments, pinning canalso partially or completely chemically transform the material of thefirst PSAB layer. Certain pinning reagents, such as hydrocarbons, formpinned PSAB layers that result in improved stress migration performanceof formed interconnects.

In one embodiment, pinning is performed by contacting the partiallyfabricated semiconductor device having a first PSAB layer (e.g.,containing Cu_(x)Si_(y)) with a third reactant to form a pinned PSABlayer. In some embodiments, the third reactant (which is also referredto as a pinning reactant) comprises a gas or a vapor selected from thegroup consisting of N₂, NH₃, a hydrocarbon, a gas from the family ofmethyl-substituted silanes, a gas from the family of methyl-substitutedamines and hexamethyldisilazane (HMDS). Mixtures of the above mentionedreactants may be also used in some embodiments. In some embodiments,pinning is plasma-assisted and is performed in a PECVD apparatus. In oneembodiment pinning is performed using NH₃ in a plasma. In anotherembodiment pinning is performed using a mixture of a hydrocarbon and NH₃(or N₂) in a plasma. In yet another embodiment, a hydrocarbon plasma canbe used in the absence of N₂ or NH₃. Inclusion of a hydrocarbon as apinning reagent was found to be associated with improvement in stressmigration characteristics of interconnects. Hydrocarbons, as usedherein, are defined as compounds with C_(x)H_(y) composition, which maybe optionally substituted with heteroatoms, such as S, N, P, etc.Hydrocarbons, as used herein include acyclic and cyclic alkanes,alkenes, alkynes, as well as amines, mercaptans, thioethers and organicphosphines. Examples of hydrocarbons that do not include heteroatoms andthat can be used as pinning reactants are methane, ethane, ethylene,acetylene, propane, propene, propyne, cyclopropane, cyclobutane,butanes, butenes, butynes, and benzene.

Note that in some embodiments, identical reagent is used duringpassivation and pinning operations, e.g., NH₃. The pinned PSAB layer, insome embodiments, includes materials, such as Si_(x)N_(y) and/orSi_(x)C_(y). In other embodiments, different materials may be formedupon pinning, depending on the chemistry of the first PSAB layer and onthe nature of intermediates and by-products formed in the firstPSAB-forming reaction.

In certain embodiments, the pinned PSAB layer has a thickness rangingfrom about 10 Å to 60 Å. The devices having pinned PSAB layers can haveresistance shifts of less than 3%, and, in some cases, less than 1%.

The stress migration parameters of interconnects can be further improvedby including a hydrogen plasma treatment into the PSAB process flow.Hydrogen plasma treatment can be performed concurrently with pinning,e.g., using a mixture of NH₃ and/or N₂ with H₂ in a plasma duringpinning. In other embodiments, hydrogen plasma treatment can beimplemented as a separate post-treatment operation performed after thePSAB layer has been pinned.

After the PSAB layer has been formed, a blanket dielectric diffusionbarrier layer is typically deposited. Dielectric diffusion barrierlayers may include silicon nitride and silicon carbide based materials,such as high carbon content silicon carbide, oxygen doped siliconcarbide, nitrogen doped silicon carbide, boron doped silicon carbide andthe like. In some embodiments deposition of a dielectric diffusionbarrier layer is performed at a temperature that is higher than thetemperature used in the PSAB formation (including passivation andpinning operations). For example, in some embodiments, PSAB formation isimplemented at a temperature under 350° C., e.g., at about 250-300° C.,while diffusion barrier deposition is performed at a temperature of atleast 350° C., e.g., 375-450° C.

In another aspect, a method of forming a PSAB layer of material includescontacting the partially fabricated semiconductor device with a PSABforming reactant to form a first PSAB layer, followed by a pinningoperation, which comprises contacting the first PSAB layer with apinning process gas in a plasma and contacting the device with H₂ in aplasma. H₂ plasma treatment can be performed concurrently with thepinning operation or subsequent to pinning, as a post-treatment step.Use of H₂ plasma treatment as a pinning reactant reduces stressmigration in the formed interconnects.

In another aspect a method of forming a PSAB layer of material includescontacting the partially fabricated semiconductor device with a PSABforming reactant to form a first PSAB layer, followed by a pinningoperation, which comprises contacting the first PSAB layer with aprocess gas comprising a hydrocarbon to form a pinned PSAB layer. Use ofhydrocarbon as a pinning reactant reduces stress migration in the formedinterconnects.

In another aspect, a semiconductor device having at least oneinterconnect is provided. The interconnect comprises an interfacebetween a metal layer and a dielectric diffusion barrier layer and aPSAB layer residing entirely within the metal layer adjacent thedielectric diffusion barrier. In one embodiment, this PSAB layercomprises Si_(x)N_(y) and/or Cu_(x)Si_(y). In other embodiments it maycomprise a material selected from the group consisting of Cu_(x)Ge_(y),Cu_(x)P_(y), Cu_(x)B_(y), Cu_(x)As_(y), Cu_(x)C_(y), Cu_(x)S_(y), Cu_(x)Se_(y), Cu_(x)Te_(y) and mixtures thereof.

In yet another aspect, an apparatus for forming a protective selfaligned buffer layer within a metal layer in a partially fabricatedsemiconductor device is provided. The apparatus includes a processchamber having an inlet for introduction of reactants; a wafer supportfor holding the wafer in position during formation of the protectiveself aligned buffer layer; and a controller comprising programinstructions for: (i) contacting the partially fabricated semiconductordevice with a nitrogen containing reactant for a period of time, whereinthe nitrogen containing reactant interacts with the exposed metalsurface of a metal layer, to form a metal nitride at the surface of saidmetal layer, thereby passivating said metal surface; and (ii)subsequently contacting the partially fabricated semiconductor devicewith a second reactant, such that the second reactant reacts withunpassivated metal atoms of the metal layer and chemically transformsthe top portion of the metal layer into a first protective self-alignedbuffer layer, wherein said buffer layer resides entirely within saidmetal layer.

These and other features and advantages of the present invention will bedescribed in more detail below with reference to the associateddrawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1E show cross sectional depictions of device structures createdduring a copper dual Damascene fabrication process.

FIGS. 2A-2B show cross sectional depictions of partially fabricateddevice structures illustrating PSAB layers.

FIGS. 3A-3C present example process flow diagrams of a PSAB-formingprocess according to some embodiments.

FIGS. 4A-4E show cross sectional depictions of device structures createdduring formation of a PSAB layer, according to some embodiments.

FIG. 5 is a schematic representation of a PECVD apparatus capable ofusing low frequency (LF) and high frequency (HF) radio frequency plasmasources that can be used for forming PSAB layers in accordance with someembodiments of present invention.

FIG. 6 is a schematic representation of one example of a multi-stationapparatus suitable for forming PSAB layers in accordance with someembodiments of present invention.

FIG. 7 is a schematic representation of another example of amulti-station apparatus suitable for forming PSAB layers in accordancewith some embodiments of present invention.

FIG. 8 is an experimental diagram, illustrating flow of reactants andplasma parameters as a function of time during PSAB-forming process.

FIG. 9 is an experimental diagram, illustrating percentage of vias withunacceptable stress migration characteristics on a wafer for differentinterconnect forming processes.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS Introduction and Overview

Formation of PSAB layers in interconnects will be illustrated in thecontext of a copper dual Damascene processing. It is understood, thatmethods disclosed herein can be used in other processing methods,including single Damascene processing, and can be applied to a varietyof metals beyond copper. For example, these methods can be applied togold and silver-containing interconnects.

Presented in FIGS. 1A-1D, is a cross sectional depiction of devicestructures created on a semiconductor substrate at various stages of adual Damascene fabrication process. A cross sectional depiction of acompleted structure created by the dual Damascene process is shown inFIG. 1E. “Semiconductor substrate” as used in this application is notlimited to the semiconductor portions of an IC device, but is broadlydefined as a semiconductor-containing substrate. Referring to FIG. 1A,an example of a partially fabricated IC structure, 100, used for dualDamascene fabrication is illustrated. Structure 100, as illustrated inFIGS. 1A-1D, is part of a semiconductor substrate, and, in someembodiments, may directly reside on a layer containing active devices,such as transistors. In other embodiments, it may directly reside on ametallization layer or on other layers that incorporate conductivematerials, e.g., layers containing memory capacitors.

A layer 103 illustrated in FIG. 1A is a layer of inter-metal dielectric,which may be silicon dioxide but is more typically a low-k dielectricmaterial. In order to minimize the dielectric constant of theinter-metal dielectric stack, materials with a k value of less thanabout 3.5, preferably less than about 3.0 and often as low as about 2.8are employed as inter layer dielectrics. These materials include but arenot limited to fluorine or carbon doped silicon dioxide,organic-containing low-k materials and porous doped silicon dioxidematerials known to those of skill in the art. Layer 103 is etched withline paths (trenches and vias) in which a partially conductive metaldiffusion barrier 105 is deposited, followed by inlaying with copperconductive routes 107. Because copper or other mobile conductivematerial provides the conductive paths of the semiconductor substrate,the underlying silicon devices and dielectric layers proximate to metallines must be protected from metal ions (e.g., Cu²⁺) that mightotherwise diffuse or drift into the silicon or inter-layer dielectricand result in degradation of their properties. Several types of metaldiffusion barriers are used in order to protect the dielectric layers ofthe IC device. These types may be divided into partially conductivemetal-containing layers such as 105 and dielectric barrier layers whichwill be described in further detail with reference to FIG. 1B. Suitablematerials for partially conductive diffusion barrier 105 includematerials, such as tantalum, tantalum nitride, titanium, titaniumnitride and the like. These are typically deposited onto a dielectriclayer having vias and trenches by a PVD method.

Copper conductive routes 107 can be formed by a number of techniques,including PVD, electroplating, electroless deposition, CVD, etc. In someimplementations, a preferred method of forming a copper fill includesdepositing a thin seed layer of copper by PVD and subsequentlydepositing bulk copper fill by electroplating. Since copper is typicallydeposited with overburden residing in the field region, a chemicalmechanical polishing (CMP) operation is needed to remove the overburdenand to obtain a planarized structure 100.

Next, referring to FIG. 1B, after the structure 100 has been completed,the surface of the substrate 100 is pre-cleaned to remove contaminantsand metal oxide. After the pre-clean, PSAB layers 108 are formed withinthe top portions of metal lines 107. Composition of PSAB layers andmethods of forming them will be described in the following sections indetail.

As depicted in FIG. 1B, a diffusion barrier film 109 is deposited on topof the PSAB layers 108 and on top of a dielectric layer 103 toencapsulate conductive routes 107. The dielectric diffusion barrier filmmay also serve as an etch stop during subsequent Damascene processing.In contrast to partially conductive barrier 105, film 109 should benon-conductive and should preferably have a low dielectric constant.Preferably materials with a dielectric constant of less than about 6,e.g., with a dielectric constant of lower than about 4 are used for adiffusion barrier film 109. Film 109 should also effectively preventdiffusion of metal into the dielectric layer and should provide etchselectivity when used as an etch stop. Conventionally, silicon nitride,and nitrogen-doped silicon carbide (NDC) were used for this application.Currently, materials with lower dielectric constants than siliconnitride are often used for this application. These materials includecarbon-rich silicon carbide materials, such as those described incommonly assigned U.S. patent application Ser. No. 10/869,474 by Yu etal., filed on Jun. 15, 2004; boron-doped silicon carbide materialsdescribed in U.S. patent application Ser. No. 10/915,117 by Yu et al.,filed on Aug. 9, 2004 and in U.S. patent application Ser. No. 11/373,847by Yu et al. filed on Mar. 8, 2006; and oxygen-doped silicon carbidematerials, e.g., described in U.S. Pat. No. 6,855,645 by Tang et al.issued on Feb. 15, 2005. Further, bi-layer and tri-layer configurationscan be employed for the diffusion barrier 109. All patent applicationsthat were mentioned in this paragraph are hereby incorporated byreference for all purposes.

The diffusion barrier film can be deposited on a semiconductor substrateby a variety of CVD-type methods. For example, plasma enhanced chemicalvapor deposition (PECVD) may be used. In some embodiments, PECVD havinga low frequency plasma component, provided by low frequencyradio-frequency (LF RF) power source, is used for diffusion barrierdeposition.

Referring again to FIG. 1B, a first dielectric layer, 111, of a dualDamascene dielectric structure is deposited on a diffusion barrier 109.This is followed by deposition of an etch stop film 113 by a PECVDmethod on the first dielectric layer 111. The dielectric layer 111 istypically composed of low-k dielectric materials such as those listedfor a dielectric layer 103. Note that layers 111 and 103 need notnecessarily have identical composition. Similarly, etch stop layer 113may or may not have an identical composition to layer 109.

The process follows, as depicted in FIG. 1C, where a second dielectriclayer 115 of the dual Damascene dielectric structure is deposited in asimilar manner to the first dielectric layer 111, onto an etch-stop film113. Deposition of an antireflective layer (not shown) and a CMP stopfilm 117 follows. Second dielectric layer 115 typically contains a low-kdielectric material such as those described above for layers 103 and111. A CMP stop film 117 serves to protect the delicate dielectricmaterial of inter-metal dielectric (IMD) layer 115 during subsequent CMPoperations. Typically, a CMP stop layer is subject to similarintegration requirements as a diffusion barrier and etch stop films 109and 113, and can similarly be composed of materials described for layer109.

The dual Damascene process continues, as depicted in FIGS. 1D-1E, withetching of vias 119 and trenches 121 in the first and second dielectriclayers. Standard lithography techniques are used to etch a patternillustrated in FIG. 1D. A trench-first or a via-first methods well knownby those of skill in the art may be employed.

Next, as depicted in FIG. 1E, these newly formed vias and trenches are,as described above, coated with a metal diffusion barrier 123, which maycontain barrier materials, such as tantalum, tantalum nitride or othermaterials that effectively block diffusion of copper atoms into thedielectric layers.

After the diffusion barrier 123 has been deposited, a seed layer ofcopper is applied (typically by a PVD process) to enable subsequentelectrofilling of the features with copper inlay. The copper layer isdeposited by electrofill and excess of metal deposited in the field isremoved in a CMP operation, performed such that CMP stops at the CMPstop film 117. FIG. 1E shows the completed dual Damascene process, inwhich copper conductive routes 124 and 125 are inlayed (seed layer notdepicted) into the via and trench surfaces over barrier 123. A PSABlayer, analogous to a PSAB layer 108 can be the formed within the topportion of the metal fill 125, and a next metallization layer may bedeposited on top of the device structure shown in FIG. 1E, if needed.

FIG. 1E depicts three Damascene interconnects, in which metal layer 107is connected with metal layer 124 of an overlying metallization layer.The role of the PSAB layer 108 in these interconnects will be presentlydescribed.

The PSAB layer 108 serves as a protective buffer between the metal layer107 and a dielectric diffusion barrier layer 109. First, the PSAB layerprotects the metal layer 107 from inadvertent oxidation. When no PSABlayer is formed, copper surface can be oxidized to copper oxide duringinadvertent exposure to oxygen or moisture in the course of devicefabrication or during end use of the device. Formation of metal oxide istypically highly undesirable since it increases resistance ofinterconnects, and, further, commonly leads to formation of voids in theinterconnect structure. Formation of voids in the copper conductor isdetrimental to the IC device and should be avoided when possible. Whiledielectric diffusion barriers, such as 109, encapsulate the metal layersand may protect them to some extent from moisture and/or oxygen duringend use, it should be noted that not all diffusion barrier materials aresufficiently hermetic to provide such protection. Further, exposure ofmetal layer to atmospheric moisture and oxygen may occur duringfabrication of an IC device. In some implementations, Damasceneprocessing may require operations that involve opening of metal layer toan ambient environment containing moisture and oxygen. For example, whenno PSAB layer is present, metal layer 107 may be exposed to atmosphereafter the vias and trenches are cut in a dielectric as shown in FIG. 1D.

Next, in some embodiments, PSAB layers can diminish electromigration atthe interface between copper lines, and dielectric diffusion barrier. Ithas been found that this interface is the most likely point of failureduring line current stress. Whereas the electromigration resistance ofcopper is high enough to sustain the wear-out in normally designedconductor lines, defect-induced electromigration failures have beenobserved at the interface between the copper and dielectric barrierlayer. For instance, wherein copper oxides or hydroxides have beenundesirably formed at such interfaces, voids will be formed in thecopper layer, which adversely affect electromigration characteristics ofsuch copper interconnects. Understandably, current density in theseregions is considerably high during actual use, thereby causingdefect-induced electromigration failure of such interconnects. PSABlayers protect metal layers from formation of defects, and therebyimprove electromigration properties of interconnects.

Further, PSAB layers can provide improved adhesion between metal layersand diffusion barrier layers. Adhesion of metal to a barrier layer is animportant characteristic of a copper interconnect. Poor adhesion mayresult in insufficient hermeticity of diffusion barrier layer and canlead to delamination of the diffusion barrier layer from an underlyingmetallization layer. Ultimately, such delamination may lead to failureof an interconnect. Generally, as dielectric constant of diffusionbarrier material is decreasing, its adhesion to an underlying metallayer becomes weaker. This is especially true for diffusion barriermaterials having high content of organic residues, such as alkyl groups,carbon-carbon bonds, etc., which generally hinder adherence to metallayers. Further, referring to barrier film stress characteristics, manybarrier materials having low dielectric constant, form films that arenot sufficiently compressive to effect good adhesion to metal layers.With these challenges in mind, it is often desirable to use PSAB layersto strengthen adhesion between metal layers and diffusion barrier layerswith low dielectric constant. In some embodiments, it may beparticularly advantageous to use PSAB layers adjacent diffusion barrierlayers with a dielectric constant less than about 4.0, e.g., about 3.5.In other embodiments, PSAB layers may be used adjacent dielectricbarrier layers with higher dielectric constant.

In a preferred embodiment, PSAB layers are formed selectively at theexposed surface of metal layers, such that other exposed materials onthe substrate surface are not affected. Typically, the PSAB layer isformed by chemical modification of the top portion of the metal layer.Advantageously, such chemical modification selectively occurs only atthe metal surface, without substantially modifying exposed surface of anadjacent layer of dielectric.

In some embodiments, a PSAB layer is formed entirely within the metallayer, such that the PSAB layer is formed to substantially the samelevel as the level of inter-layer dielectric adjacent the metal layer.This embodiment is illustrated in FIG. 2A, which presents across-sectional depiction of a partially fabricated semiconductordevice. In this device, vias and trenches formed in an inter-layerdielectric 201, are lined with diffusion barrier material 203 and arefilled with metal 205. The top portion of metal is selectively convertedto a PSAB layer 207, such that the PSAB layer 207 is substantially atthe same level as the layer 201. Thus, layer 207 does not extendvertically higher than the level of surrounding dielectric 201. This canbe accomplished, by impregnating metal layer with PSAB material throughchemical transformation of metal atoms. In some embodiments, nosubstantial deposition of material on top of the metal layer occursduring PSAB layer formation. In other embodiments, some material can bedeposited or adsorbed on the surface of the metal layer, and later beconsumed through diffusion into the metal layer and/or subsequentchemical reaction with metal atoms. Thus, in some embodiments, PSABlayer does not extend higher than 10 Å, preferably not higher than 5 Åabove the level of dielectric 201 or the level of metal layer 205 priorto PSAB formation. After the PSAB layer has been formed, a blanket layerof dielectric diffusion barrier 209 is deposited over the substratesurface.

Yet in other embodiments, PSAB layer may extend higher than the layer ofadjacent inter-layer dielectric. This can occur when in addition tochemical conversion of metal surface, a substantial amount of depositiononto the metal surface occurs during formation of the PSAB layer. Theseembodiments are illustrated by FIG. 2B, which shows a cross sectionaldepiction of a device, in which a PSAB layer 207 is higher than thelevel of dielectric 201 or the level of metal in metal line 205 prior toformation of the PSAB layer.

In both embodiments illustrated in FIG. 2A and FIG. 2B, PSAB layer 207may have a multi-layer structure. Layers 207 may have two or moresublayers (not shown) which may have a distinct or gradually changingcomposition. For example layer 207, may have a bottom sublayerpredominantly composed of Cu_(x)Si_(y), and a top sublayer predominantlycomposed of Si_(x)N_(y). In some embodiments, concentration ofSi_(x)N_(y) is gradually decreasing as the distance from the dielectricdiffusion barrier is increasing. Such sublayers may be formed bytransforming the top portion of the first-formed PSAB layer. Forexample, the top portion of PSAB layer may be modified by atransformation, effected by chemical treatment, plasma treatment,thermal treatment or some combination of these treatments.

In some embodiments, the first-formed PSAB layer (containing, e.g.,Cu_(x)Si_(y)) is entirely transformed to a modified PSAB layer, withoutforming sublayers of material. A particular chemistry and amount of suchmodification is tailored to a particular application for a PSAB layer.In some embodiments, chemical modification of the first-formed PSABlayer may be necessary to control the thickness of PSAB layer. Further,in some embodiments, it may be advantageous to transform thefirst-formed PSAB layer or its top portion to a material that providesoptimal adhesion with a dielectric diffusion barrier. Some of suchmaterials include silicon nitride, silicon carbide, hydrogen-dopedcarbon, and their various doped modifications.

It should be noted that in certain embodiments, the PSAB layer has agraded composition. The PSAB layer may be viewed as an alloy of coppermetal with PSAB material, or as a layer of copper impregnated with PSABmaterial at an interface with a dielectric diffusion barrier layer. Theconcentration of elemental copper in these embodiments is graduallydecreasing towards the interface with the diffusion barrier layer, whileconcentration of PSAB material (often dielectric) is increasing. Suchstructure is particularly advantageous for improvement of adhesionbetween metal and dielectric layers, as gradual change in materialproperties leads to good binding between the two layers. While in someembodiments, PSAB layers are graded, in other embodiments PSAB layersmay be distinct rather than blended into the underlying metal layers,and may have an abrupt boundary with the metal layer.

While PSAB layers provide numerous advantages to interconnect structureand performance, controlled formation of these layers presents severalchallenges. PSAB layers typically contain materials having lowconductivity, and, therefore, PSAB presence increases resistance ofinterconnects. Since such increase in resistance is undesirable, it isimportant to control thickness of PSAB layers, so that it does notexceed the thickness that is necessary for a particular application.Inadvertent formation of unnecessarily thick PSAB layers may increaseinterconnect resistance to levels that may not be acceptable in theindustry. The challenges of preparing thin PSAB layers become morepronounced as the dimensions of features in IC devices continue todecrease. It is, for example, difficult to control PSAB layer thickness,and hence, interconnect resistance in metal lines that are only about1000 Å deep. Methods of forming controlled amounts of PSAB materials areprovided herein. These methods can be applied to IC substrates having awide range of feature sizes, but may find particular use for IC devicefabrication at 90 nm technology node and at more advanced nodes. Forexample, these methods may be particularly useful for fabricatingdevices, in which thickness of a single metallization layer does notexceed 1000 Å

Methods of Forming PSAB Layers

Thickness of PSAB layers and, consequently, resistance of interconnectscan be controlled by modulating several parameters of the PSAB formationprocess. For example, amount of first formed PSAB material can becontrolled by modulating the conditions of reaction that transformsmetal atoms into a first PSAB material, e.g., temperature, reactant flowrate, reactant contact time etc. Further, thickness of PSAB layer can becontrolled by limiting the diffusion of non-conductive materialsgenerated during PSAB layer formation down the metal line. This can beaccomplished by modifying the first-formed PSAB layer in a special“pinning” operation. Finally, it was unexpectedly discovered that it ispossible to partially passivate the metal surface prior to PSAB layerformation, and thus limit the amount of first-formed PSAB material onthe surface of the metal.

In some embodiments, a passivating reagent, e.g., NH₃ converts a certainfraction of metal atoms on an exposed surface of a metal layer to apassivated material. For example, treating the metal surface with anitrogen-containing reagent, can convert elemental metal to metalnitride, thereby depleting the amount of metal atoms that are availablefor formation of a PSAB layer, and therefore essentially, passivatingthe metal surface towards the PSAB-forming reaction. In differentembodiments passivation may be accomplished by different mechanisms. Forexample, in some embodiments, the passivating reagent may chemicallytransform a fraction of metal layer surface. In other embodiments, thepassivating reagent may be adsorbed on a surface of metal layer, therebydecreasing the fraction of exposed metal atoms. Yet in other embodimentspassivation may involve formation of a passivated layer (e.g., throughchemical transformation or adsorption) that blocks the diffusion of PSABmaterial down the metal line.

Without being bound by a particular mechanism or theory of operation, itis herein provided that treatment of a partially fabricated IC devicewith certain passivating reagents prior to formation of the PSAB layeropens a possibility for controlling the thickness of PSAB layers. Thegreater the amount of passivated material formed at the metal surface,the smaller is the amount of subsequently formed PSAB material and,consequently, the smaller is the thickness of PSAB layer, and resistanceof an interconnect The degree of passivation can be controlled bymodulating the conditions of passivation process, such as the nature ofpassivating reagent, the temperature during passivation, the flow rateof the passivating reagent and its contact time with the metal surface.Passivation operation is performed, in some embodiments, preferablywithout igniting plasma.

Fabrication of interconnects using a process that includes partialpassivation of the metal surface prior to formation of PSAB layer, mayresult in products that have a resistance shift of less than 3% and, insome cases less than 1%. For example, resistance shift of less thanabout 1% has been observed for devices at a 90 nm node, and resistanceshift of less than about 3% has been observed for devices at a moreadvanced 65 nm node. Resistance shift is a difference between resistanceof analogous interconnects with and without a PSAB layer measured atidentical conditions. The process of forming interconnects withcontrolled resistance is illustrated by the process flow diagramspresented in FIGS. 3A-3C, and by cross-sectional views of devicestructures presented in FIGS. 4 A-E. Referring to FIG. 3A, the processstarts by providing a partially fabricated semiconductor device having apattern of exposed metal layers in a dielectric, as shown in processblock 301. The substrate is provided after the vias and trenches havebeen filled with metal and excess metal has been removed by CMP.Examples of such substrate are illustrated in FIG. 1A and in FIG. 4A. InFIG. 4A, a via and a trench formed in an inter-layer dielectric 401 arelined with a diffusion barrier 403, and are filled with a metal fill405. The substrate is planarized by CMP prior to formation of the PSABlayer.

In some embodiments, the entire process shown in FIG. 3A is performed ina vacuum environment, without breaking the vacuum or exposing thepartially fabricated device to an ambient atmosphere during or betweenthe operations shown in FIG. 3A. In some embodiments, the entire processdepicted in FIG. 3 is performed in one apparatus. Further, in someembodiments, the entire process depicted in FIG. 3A can be performed atone station of a multi-station apparatus. In some embodiments, H₂ plasmapost-treatment shown in process block 310 is performed at a differentstation than operations 301-309, because, a different temperature may berequired in order to optimize the impact of the H₂ post treatmentprocess. Generally, the process shown in FIG. 3A can be performed at atemperature ranging from about 20° C. to 500° C., and at a pressureranging from about 10 mTorr to about 100 Torr. The flow rates ofreactants in the process can range from about 0.001 sccm to about 10000sccm (per process chamber housing four 300 mm wafers), and reactantcontact times can range from about 0.5 to about 50000 seconds, e.g. fromabout 0.5 to about 5000 seconds.

PSAB layer can be formed in any apparatus that provides mechanisms forreagent flow and a process chamber that can effectively isolate thefabricated device from moisture and oxygen of ambient environment.Preferably the apparatus should be capable of providing vacuumenvironment and a temperature that is necessary to perform thePSAB-forming reaction. For example, various types of CVD tools can beused for PSAB layer formation. In some embodiments, the PSAB-formingprocess may include operations that require plasma treatment, orplasma-enhanced reactions. Therefore, in some embodiments it ispreferable to use PECVD tools, such as SEQUEL™ and VECTOR™ PECVD toolsavailable from Novellus Systems, Inc. (San Jose, Calif.). Further, insome embodiments, a dual frequency PECVD apparatus that has highfrequency (HF) and low frequency (LF) radio frequency (RF) plasmasources, is preferred. Low frequency RF power refers to RF power havinga frequency between 100 kHz and 2 MHz. A typical frequency range for LFplasma source is between about 100 kHz to 500 kHz, e.g., 400 kHzfrequency may be used. High frequency power refers to RF power with afrequency greater than 2 MHz. Typically HF RF frequency lies in therange of between about 2 MHz-30 MHz. A commonly used HF RF valuesinclude 13.56 MHz and 27 MHz. In some embodiments LF power ranging fromabout 0 W/cm² to 1.0 W/cm², and HF power ranging from 0.1-1.5 W/cm² canbe used in plasma assisted operations, such as during pre-clean, pinningand H₂ post-treatment. In some embodiments a single frequency process isused in plasma-assisted operations.

Referring again to FIG. 3A, the substrate is provided to a processchamber and is optionally pre-cleaned as shown by the process block 303.Pre-cleaning operation removes contaminants from the surface of thewafer. In particular, pre-cleaning can remove metal oxide from the metalsurface, thereby exposing metal atoms for subsequent reactions. It isdesirable to perform pre-cleaning after a CMP operation or any exposureto moisture and oxygen, since CMP can leave a significant amount ofcontaminants on a wafer surface. Pre-clean operation can be accomplishedby, for example, exposing the surface of a substrate to a plasmacontaining a reducing gas, such as NH₃ or H₂. In some embodimentspre-clean with H₂ plasma has provided devices with particularly improvedcharacteristics. The process gas during pre-clean can also include acarrier gas, such as N₂, He, Ar, etc. In one example, pre-clean isperformed in a PECVD chamber at a temperature of about 200-400° C.,pressure of about 1.5-4 Torr and an H₂ flow rate of about 4000-10000sccm. The plasma, which may contain an HF and an LF component is ignitedand is sustained at a total power of 200-1000 W per one 300 mm wafer. Insome embodiments, it is preferable to use HF power at 0.1-1.5 W/cm² andLF power at 0-0.8 W/cm² during the pre-clean operation. In anotherexample, NH₃ is used instead of H₂ as a reducing gas, and is flowed intothe process chamber at a flow rate ranging from about 6000 to 8000 sccm.An N₂ carrier gas is flowed into the chamber at a flow rate of about2000-4000 sccm. The pre-cleaning treatment can last several seconds,e.g., between about 6-20 seconds.

After the contaminants and metal oxides are removed from the surface ofthe substrate, the substrate is contacted with a passivating reagent. Insome embodiments, the passivating reagent is a nitrogen-containingreagent that is capable of forming metal nitride, e.g., Cu_(x)N_(y) atthe surface of the metal layer, as shown in the process block 305. In aparticular embodiment, the nitrogen-containing reagent is NH₃.Generally, a variety of nitrogen-containing compounds can be used. Theseinclude hydrazine (N₂H₂) and amines (e.g., methylamine, ethylamine,diethylamine, etc.). In some embodiments halogens or halogen-containingcompounds may be used as passivating agents, partially converting metalsurface to metal halides. For example, I₂ can be used. In otherembodiments certain hydrocarbons may be used as passivators, partiallyconverting the metal surface to metal carbide. The passivating reagentis preferably selected such that it can modify metal surface without theuse of plasma. In one embodiment, the passivating reagent is introducedin a controlled fashion, such that the metal surface is not entirelyconverted to passivated material, but still contains unpassivated metalatoms, which can be converted to a PSAB material during subsequent PSABforming operation. A substrate having a partially passivated surface isillustrated in FIG. 4B. In this example metal nitride 407 is formedwithin an upper portion of metal layer 405. Metal nitride 407 occupiesonly a fraction of exposed surface, with a certain amount of metal 405being available to subsequent transformations. The degree of passivationof the metal surface, can be controlled by parameters of the passivatingprocess, such as nature of the passivating reagent, temperature, flowrate of passivating reagent and contact time of reagent with the metallayer.

In one embodiment, copper surface is partially converted to Cu_(x)N_(y)by flowing NH₃ into a process chamber at a flow rate of about 6000-8000sccm, at a pressure of about 1.5-4 Torr and at a temperature of about200° C.-400° C. In this embodiment, plasma is not ignited during thepassivation process. In other embodiments, passivation may beplasma-assisted. In some embodiments NH₃ is the only gas that is flowedinto the chamber during passivation operation. In other embodiments, NH₃or other passivating reagent may be diluted by a carrier gas, such asN₂, H₂, He, Ar, etc. The metal layer is contacted with the passivatingreagent for a controlled period of time that provides the desired amountof passivated material at the metal surface. For example, the substratecan be treated with NH₃ for about 2-4 seconds to convert a desiredfraction of copper surface to copper nitride.

In one embodiment, the passivating operation selectively transformsmetal surface without affecting other exposed surfaces of the substrate.For example, passivating operation 305 in this embodiment does nottransform the dielectric layer and does not deposit any material on alayer of dielectric.

Referring again to FIG. 3A, the PSAB process follows by forming a firstPSAB layer within the top portion of the metal layer. As shown in theprocess block 307, the partially fabricated device is contacted with asecond reactant to form a first PSAB layer. The second reactant reactswith the available metal atoms of the metal layer, but preferably doesnot affect materials elsewhere on the wafer (e.g., does not react ordeposit any material on a dielectric layer), and does not react with thepassivated material. Consequently, the depth of the first PSAB layercorrelates with the amount of passivated material formed duringoperation 305, such that increased amount of passivated material at themetal surface leads to decreased thickness of the PSAB layer. Therefore,the thickness of the PSAB layer and resistance of interconnect iscontrolled by the amount of passivated material formed in operation 305,or, rather by the amount of unpassivated metal atoms that remainavailable for transformation. For example, if all of the metal atoms atthe metal surface are converted to passivated material, such asCu_(x)N_(y), the PSAB layer would not form, while if no passivatingoperation precedes PSAB-forming operation 307, the first-formed PSABlayer may be excessively thick, thereby unnecessarily increasinginterconnect resistance.

In some embodiments the second reactant (also referred to asPSAB-forming reactant) comprises a gas or a vapor, selected from thegroup consisting of SiH₄, GeH₄, PH₃, B₂H₆, AsH₃, an alkane, H₂S, H₂Se,and H₂Te. Further, a variety of metal hydrides and alkylated elementhydrides can be used. Examples include SnH₃, SbH₃, and RGeH₃, R₂GeH₂,R₃GeH, wherein R is an alkyl substituent, which can be furthersubstituted with heteroatoms, such as N, P, and S. In some embodiments,metal halides (fluorides, chlorides, bromides or iodides) are used forforming PSAB layers. For example, in some embodiments, molybdenumhalides are used. In these cases, inter-metal compounds and alloys (e.g.Cu_(x)Mo_(y)) are formed as first PSAB layers. In general, a variety ofmetal hydrides and/or halides or alkyl substituted hydrides and/orhalides which could be delivered into a CVD chamber in their gaseousforms could be employed as PSAB forming reactant. Further, in someembodiments, a variety of metal containing compounds (includingorganometallics) that could be delivered into the CVD chamber in itsgaseous form could be used as PSAB forming reactants. Examples includealkyl, carbonyl, and cyclopentadienyl-substituted organometalliccompounds, such as tetrakisdimethylaminotitanium, cyclopentadieneylmolybdenum, nickel tetracarbonyl and iron pentacarbonyl. Typically, suchcompounds would impregnate top portions of copper lines with thin layersof metals, e.g., Ti, Mo, Ni, Fe and the like to form alloys with copper.

The second reactant (PSAB-forming reactant) contacts the semiconductorsubstrate under such conditions that top portion of the metal isconverted to a first PSAB layer, comprising a material selected from thegroup consisting of M_(X)Si_(y), M_(x)Ge_(y), M_(x)P_(y), M_(x)B_(y),M_(x)As_(y), M_(x)C_(y), M_(x)S_(y), M_(x)Se_(y), and M_(x)Te_(y), whereM is metal, when SiH₄, GeH₄, PH₃, B₂H₆, AsH₃, an alkane, H₂S, H₂Se, andH₂Te reactants are used. For example a layer comprising Cu_(x)Si_(y),Cu_(x)Ge_(y), Cu_(x)P_(y), Cu_(x)B_(y), Cu_(x)As_(y), Cu_(x)C_(y),Cu_(x)S_(y), Cu_(x)Se_(y), or Cu_(x)Te_(y) is formed. While in someembodiments formation of the first PSAB layer may be plasma-assisted, inmany embodiments, including an embodiment in which SiH₄ contacts Cu toform Cu_(x)Si_(y), plasma is preferably not ignited during formation ofthe first PSAB layer. When plasma is not applied, silane selectivelyreacts with metal surface, without depositing any material on otherexposed surfaces of the wafer. For many PSAB forming reagents plasmashould not be ignited during PSAB forming process, in order to achieveselective formation of PSAB layer within the metal surface, rather thanblanket deposition of material across the wafer.

In some embodiments, the first PSAB layer is formed entirely within thetop portion of the metal line. Such embodiment is illustrated in FIG.4C, where the first PSAB layer 409 is self-aligned with the metal layer405 and does not extend higher than the layer of surrounding dielectric401. Layer 409 comprises, in one embodiment, metal silicide and metalnitride remaining from the passivating treatment (not shown). Layer 409can also include metal (in zero oxidation state), which is impregnatedwith the above-mentioned materials.

In a particular example, the first PSAB layer is formed by flowing SiH₄into a process chamber at a flow rate of about 100-1000 sccm. NH₃ at aflow rate of about 4000-10000 sccm or H₂ at a flow rate of about4000-10000 sccm can be optionally flowed into the process chamberconcurrently with silane. The SiH₄ treatment lasts for about 1-6 secondsat a temperature ranging from about 200-400° C. and pressure rangingfrom about 1.5-4 Torr. In some embodiments, it is preferable to keep thetemperature lower than 300° C. in order to limit diffusion ofnonconductive species into the metal line. In other embodiments,temperatures higher than 300° C. are used while diffusion ofnonconductive species and via resistance are controlled using othermethods (e.g., passivation and pinning). No plasma is applied in thisembodiment, and SiH₄ selectively reacts only with the metal surface toform a copper silicide containing PSAB first layer

In an alternative embodiment, the first PSAB layer may be formed bytreating the substrate with a surface active reagent that selectivelyadsorbs on a metal surface. This embodiment is described in detail inU.S. application Ser. No. 10/980,076, which was previously incorporatedby reference.

Some issues surrounding PSAB layer formation will be illustrated withreference to Cu_(x)Si_(y) first PSAB layer. It is understood, thatsimilar considerations may also apply to PSAB layers with othercompositions.

When copper surface is contacted with silane at a certain temperature(e.g., between about 200° C.-400° C.), silane catalyitically decomposesat copper surface to form elemental silicon, which diffuses into thecopper layer and slowly reacts with copper atoms to form Cu_(x)Si_(y).Copper atoms that initially serve as a catalyst for silane decompositioneventually undergo a transformation to copper silicide, which is themain component of the first formed PSAB layer. In this scenario, a largeamount of elemental silicon is initially formed in operation 307.Passivation of copper layer in operation 305 reduces the fraction ofcatalytic copper atoms in the zero oxidation state at the exposedsurface, and thereby reduces the amount of elemental silicon that isinitially formed. Passivation, in certain embodiments, may also play arole in limiting the diffusion of elemental silicon into the copperline. Therefore, passivation reduces the thickness of the first PSABlayer and provides a way to control resistance of PSAB-containinginterconnects.

In some embodiments, it may also be desirable to further control thediffusion of elemental silicon (or other non-conductive material) intothe metal lines. Diffusion of large amounts of non-conductive materialinto the metal line leads to unwarranted increase in metal lineresistance which is controlled, in some embodiments, by an optional“pinning” operation shown in the process block 309 of FIG. 3. “Pinning”operation forms a dielectric cap on or within the first PSAB layer, andserves to limit the diffusion of non-conductive reaction intermediatesor by-products into the depth of metal lines by converting them to amaterial that does not readily diffuse into the metal. Further,“pinning” operation may transform unstable phases of copper silicide orcopper nitride to a more stable material. Even further, “pinning”operation forms a cap of dielectric material that has good adhesion withdielectric diffusion barrier materials. It is, therefore, oftenadvantageous to form a “pinned” PSAB layer to improve such adhesion.“Pinning operation” is referred to as a “dielectric cap” formation inU.S. application Ser. No. 10/980,076, from which the current applicationclaims priority. Further, in certain embodiments, pinning operation mayreduce stress migration parameters of formed interconnects.

As shown in the process block 309 of FIG. 3, pinned PSAB layer is formedby contacting the device substrate with a reactant. In general, pinningcan be accomplished by thermal treatment, plasma treatment, chemicaltreatment, or some combination of the three. In one embodiment, pinningis performed by contacting the substrate with a pinning reagent selectedfrom the group consisting of N₂, NH₃, a hydrocarbon, a gas from thefamily of methyl-substituted amines, and mixtures thereof. In someembodiments silicon-containing pinning reagents, such as a gas from thefamily of methyl-substituted silanes or HMDS may be used. Preferably,modification of the first PSAB layer with the pinning reagent isperformed with plasma treatment. In one embodiment, the first PSAB layercontaining Cu_(x)Si_(y) is treated with NH₃ in a plasma. Underconditions practiced in this embodiment, excess of elemental siliconresiding within and/or on the surface of metal line is transformed intosilicon nitride, which does not readily diffuse into the bulk of metallayer. Further, under conditions of such pinning, Cu_(x)Si_(y) ispartially or completely transformed to copper metal (at zero oxidationstate) impregnated with silicon nitride, thereby forming an excellentadhesive layer at the interface of metal fill and a dielectric diffusionbarrier.

In a particular example, a substrate having a Cu_(x)Si_(y) first PSABlayer is treated with NH₃ and N₂ in a plasma generated using HF and LFpower sources. NH₃ is introduced into a process chamber at a flow rateof about 6000-8000 sccm. N₂ is flowed into the chamber at a flow rate ofabout 2000-4000 sccm. The substrate is treated at a temperature of about200-400° C., and pressure of about 1.5-4 Torr for a period of timeranging from about 3 to 20 seconds. Plasma is ignited using HF and LFpower sources at a total power level of about 200-1000 W for one 300 mmwafer. As a result, a pinned PSAB layer containing Si_(x)N_(y) isformed.

Note that in some embodiments the same reagent may be used during thepassivation operation 305 and a pinning operation 309. For example, insome embodiments, NH₃ is used as a passivating reagent without use ofplasma and as a pinning reagent in a plasma-enhanced process. Further,in some embodiments, NH₃ is also used in the pre-cleaning step and as anauxiliary gas during formation of the first PSAB layer.

In some embodiments, (including embodiments employing hydrocarbon andsilicon containing pinning reagents) pinning conditions are preferablyselected such that only the first PSAB layer is transformed, while nosubstantial deposition occurs elsewhere on the wafer, e.g., on adielectric field. Preferably, in these embodiments no more than 10 Å ofmaterial is deposited elsewhere on the dielectric field regions of thewafer.

Depending on a reagent that is used in pinning, the pinned PSAB layermay contain Si_(x)N_(y), Si_(x)C_(y), hydrogen-doped carbon or acombination of these materials. For example, treatment with hydrocarbonswill result in Si_(x)C_(y) or C:H-containing pinned PSAB layer, whiletreatment with NH₃ and N₂ will result in Si_(x)N_(y) containing pinnedPSAB layer. FIG. 4D illustrates a cross-section of a device having apinned PSAB layer 411. In this example, pinning has transformed anentire first PSAB layer to a pinned layer having a differentcomposition. In this example pinned PSAB layer resides entirely withinthe top portion of the metal line 405 and does not extend higher thanthe level of surrounding dielectric 401. In other embodiments, pinningmay result in a layer that is higher than the layer of surroundingdielectric. For example, if substantial amount of elemental siliconformed on the surface of metal layer 405 is transformed to siliconnitride, the pinned PSAB layer (or a dielectric cap) may be higher thanthe level of surrounding dielectric. In some embodiments, the entirefirst PSAB layer is transformed to a pinned PSAB layer. For example, allof the copper silicide of the first PSAB layer may be converted tosilicon nitride. In other embodiments, certain amounts of material ofthe first PSAB layer may not be transformed during pinning. For example,certain particularly stable phases of copper silicide may remain in thepinned PSAB layer. Yet, in other embodiments, only the top portion ofthe first PSAB layer may be transformed by pinning (partially orcompletely), thereby forming a bi-layer structure. For example, thepinned PSAB layer may have a bottom layer that contains copper silicide,and a top layer that contains silicon nitride. Typically concentrationsof components gradually change within the PSAB layers, thereby providingfor good adhesion between metal and a dielectric.

In some cases, pinning using hydrocarbons was found to be associatedwith improvement in stress migration parameters of interconnects.Hydrocarbons, as used herein, are defined as compounds with C_(x)H_(y)composition, which may be optionally substituted with heteroatoms, suchas S, N, P, etc. Hydrocarbons, as used herein include acyclic and cyclicalkanes, alkenes, alkynes, as well as amines, mercaptans, thioethers andphosphines. Examples of hydrocarbons that do not include heteroatoms andthat can be used as pinning reactants are methane, ethane, ethylene,acetylene, propane, propene, propyne, cyclopropane, cyclobutane,butanes, butenes, butynes, and benzene.

Pinning with hydrocarbons results in chemical transformation of thefirst PSAB layer leading to a structure with slower migration ofvacancies in a via.

In some embodiments, pinning is performed exclusively with hydrocarbonsin a plasma without NH₃, N₂ and other pinning reagents. In otherembodiments, mixtures of pinning reagents (e.g., NH₃, N₂,) with ahydrocarbon may be used during plasma-assisted pinning. Hydrocarboncontent in the process gas can range from about 0.0001% (trace values)to 100%, preferably from about 1% to 100% by volume. Pressure,temperature, and plasma conditions for hydrocarbon pinning can besimilar to those described above for NH₃ pinning. In one embodiment thefirst PSAB layer is treated with a mixture of NH₃ (or N₂) flowed intothe process chamber at the flow rate range of between about 500 sccm to5000 sccm and cyclopropane flowed in the range of 2.5 sccm to 5000 sccmper one 300 mm wafer using a plasma. When such treatment is performed onCu_(x)Si_(y) PSAB layer containing a Si_(x)C_(y)N_(z) material istypically formed.

In another embodiment a hydrocarbon is flowed into the process chamberwithout being mixed with other pinning reagents. For example,cyclopropane can be flowed into the chamber at a flow rate ranging fromabout 2.5 to 5000 sccm per one 300 mm wafer. The plasma is then ignitedunder similar conditions or under slightly modified conditions, asdescribed for NH₃ pinning and the first PSAB layer is modified byhydrocarbon pinning. When such treatment is performed on Cu_(x)Si_(y)PSAB layer containing a Si_(x)C_(y) material is typically formed.

It was also found that treatment of PSAB layer's with H₂ plasma duringor after pinning improves stress migration characteristics ofinterconnects. H₂ plasma chemically modifies the surface of the PSABlayer and leads to structures with lower stress migration, presumablyalso by slowing the migration of vacancies within the via. In someembodiments H₂ is included into the process gas used during pinning.Examples of mixtures of pinning reagents with H₂, which can be usedinclude: NH₃ and H₂; N₂ and H₂; NH₃, N₂, and H₂; hydrocarbon, NH₃, andH₂; hydrocarbon, N₂, and H₂. In one embodiment, H₂ plasma treatment isused instead of pinning (no other pinning reagents added). Othercombinations of pinning reagents (e.g., ternary mixtures) with hydrogenmay be used, as will be understood by those of skill in the art. H₂ canbe supplied into the process chamber at a flow rate ranging from 40 to20000 sccm per four 300 mm wafers or 10 to 5000 sccm per one 300 mmwafer. In some embodiments H₂ comprises at least 0.01% of the total gasflow during pinning, preferably between 1 and 50%. Plasma, temperature,and pressure conditions for pinning which includes H₂, can be similar tothose listed for NH₃ pinning.

In some embodiments, H₂ plasma treatment is performed after the pinningoperation is completed, as shown by process block 310 of FIG. 3A. DuringH₂ plasma post-treatment, H₂ can be supplied to the process chambereither alone or concurrently with inert carrier gas at a flow rateranging from about 40 to 20000 sccm per four 300 mm wafers or 10 to 5000sccm per one 300 mm wafer. Plasma, temperature, and pressure conditionsfor H₂ post-treatment can be similar to those listed above for NH₃pinning operation.

FIGS. 3B and 3C present process flow diagrams for specific examples ofPSAB forming processes. In these and other embodiments the passivationoperation 303 may be optional. Referring to FIG. 3B, the process startsas described previously by providing a partially fabricatedsemiconductor device having a pattern of metal layers in a dielectric,in process block 301. The device is optionally pre-cleaned with plasmain operation 303 and, the metal layer is optionally passivated using apassivating reactant (e.g., a nitrogen-containing passivating reactant)without use of plasma in an operation 311. Then the device is contactedwith a PSAB forming reactant, such as SiH₄, GeH₄, B₂H₆ or H₂S withoutuse of plasma to form a first PSAB layer in an operation 313. Finally,the device is contacted with a hydrocarbon and optionally with H₂ in aplasma to form a pinned PSAB layer in an operation 315. In otherembodiments the PSAB process may end with pinning using NH₃ and H₂ in aplasma, hydrocarbon and NH₃ in a plasma, or with pinning using otherreactant combinations as described above.

In an embodiment described in a process flow diagram of FIG. 3C, theprocess flows analogously to the process shown in FIG. 3B untiloperation 313. After formation of the first PSAB layer in operation 313,the device is treated with a pinning reagent in a plasma to form apinned PSAB layer in operation 317. Examples of pinning reagents includeN₂, NH₃, a hydrocarbon, a gas from the family of methyl-substitutedsilanes, a gas from the family of methyl-substituted amines, HMDS, andmixtures thereof. After pinning, the flow of the pinning reactant isstopped, and the device is subjected to H₂ plasma post-treatment asshown in the process block 319.

After the pinned and/or H₂ treated PSAB layer is formed, a dielectricdiffusion barrier layer is deposited on top of the PSAB layer 411 and adielectric 401. Cross-sectional depiction of a resulting structure isshown in FIG. 4E. Dielectric diffusion barrier layer is preferablydeposited in the same vacuum environment as the PSAB layer, withoutexposing the substrate to moisture or oxygen. In some embodiments thedielectric diffusion barrier is deposited in the same process chamber inwhich the PSAB layer has been deposited, e.g., in a process chamber of aPECVD apparatus. The dielectric diffusion barrier may include, forexample, silicon carbide based materials, such as silicon carbide, whichmay be doped with nitrogen, oxygen, boron etc. In some embodiments it isparticularly desirable to use low-k diffusion barrier layers formed ontop of PSAB-capped lines and ILD. In one embodiment use of oxygen dopedsilicon carbide (ODC) is particularly preferred. ODC material typicallyhas a low dielectric constant (e.g., less than 4.0), and is therefore adesired diffusion barrier material. However, in the absence of PSABcapping, direct deposition of ODC layers on top of copper lines,resulted in oxidation of copper and deterioration of interconnectproperties. PSAB technology allows use of ODC diffusion barrier formedon top of PSAB layer, since copper is protected from oxidation by PSABmaterial. ODC layers can be formed by PECVD using silicon, carbon, andoxygen-containing precursors.

In some embodiments deposition of a dielectric diffusion barrier layeris performed at a temperature that is higher than the temperature usedin the PSAB formation (including passivation and pinning operations).For example, in some embodiments, PSAB formation is implemented at atemperature under 350° C., e.g., at about 250-300° C., while diffusionbarrier deposition is performed at a temperature of at least about 350°C., e.g., 375-450° C.

After the diffusion barrier has been deposited, an interconnect may beformed using conventional Damascene processing, such as described withreference to FIGS. 1A-1E.

The methods described above provide interconnects with controllableresistance and/or improved stress migration characteristics. Thethickness of PSAB layers formed by these methods can range from about 10Å to 10000 Å. It is especially advantageous that these methods providecontrol over thickness of PSAB layers in the range of about 10-100 Å,particularly at a 10-60 Å range. PSAB films ranging in thickness fromabout 10-60 Å can provide interconnects with particularly smallresistance shifts of less than 1% and less than 3%, that are currentlydemanded in the IC industry.

Further, introduction of passivating operation into a PSAB formingprocess provides a greater working range for other parameters of theprocess. For example, diffusion of non-conducting material into the bulkof metal layer was minimized by using a relatively low temperature ofless than about 280° C. during formation of the first PSAB layer. Withthe use of passivating technique, diffusion control may becomerelatively less important, and temperatures higher than 280° C., e.g.,between about 300-400° C. can be used. It is understood, however, thatin other embodiments, diffusion control may still remain important andformation of first PSAB layer may be optimal at about 250-300° C.

Apparatus

The present invention can be implemented in many different types ofapparatus, such as chemical vapor deposition (CVD) reactors andspin-coating systems. Generally, the apparatus will include one or morechambers or “reactors” (sometimes including multiple stations) thathouse one or more wafers and are suitable for wafer processing. Eachchamber may house one or more wafers for processing. The one or morechambers maintain the wafer in a defined position or positions (with orwithout motion within that position, e.g. rotation, vibration, or otheragitation). In one embodiment, a wafer undergoing the PSAB layer andbarrier layer deposition is transferred from one station to anotherwithin the reactor during the process. While in process, each wafer isheld in place by a pedestal, wafer chuck and/or other wafer holdingapparatus. For certain operations in which the wafer is to be heated,the apparatus may include a heater such a heating plate. In a preferredembodiment of the invention, a PECVD system may be used. In even morepreferred embodiments the PECVD system includes a LF RF power source.

FIG. 5 provides a simple block diagram depicting various reactorcomponents arranged for implementing the present invention. As shown, areactor 500 includes a process chamber 524, which encloses othercomponents of the reactor and serves to contain the plasma generated bya capacitor type system including a showerhead 514 working inconjunction with a grounded heater block 520. A high-frequency RFgenerator 502 and a low-frequency RF generator 504 are connected to amatching network 506 that, in turn is connected to showerhead 514.

Within the reactor, a wafer pedestal 518 supports a substrate 516. Thepedestal typically includes a chuck, a fork, or lift pins to hold andtransfer the substrate during and between the deposition reactions. Thechuck may be an electrostatic chuck, a mechanical chuck or various othertypes of chuck as are available for use in the industry and/or research.

The process gases are introduced via inlet 512. Multiple source gaslines 510 are connected to manifold 508. The gases may be premixed ornot. Appropriate valving and mass flow control mechanisms are employedto ensure that the correct gases are delivered during the pre-cleaning,passivation, PSAB formation and pinning phases of the process. In casethe chemical precursor(s) is delivered in the liquid form, liquid flowcontrol mechanisms are employed. The liquid is then vaporized and mixedwith other process gases during its transportation in a manifold heatedabove its vaporization point before reaching the deposition chamber.

Process gases exit chamber 500 via an outlet 522. A vacuum pump 526(e.g., a one or two stage mechanical dry pump and/or a turbomolecularpump) typically draws process gases out and maintains a suitably lowpressure within the reactor by a close loop controlled flow restrictiondevice, such as a throttle valve or a pendulum valve.

In one of the embodiments a multi-station apparatus may be used forforming a PSAB layer and a diffusion barrier. The multi-station reactorallows one to run different processes concurrently in one chamberenvironment, thereby increasing the efficiency of wafer processing. Oneexample of such an apparatus is depicted in FIG. 6. A schematicpresentation of top view is shown. An apparatus chamber 601 comprisesfour stations 603-609. In general, any number of stations is possiblewithin the single chamber of a multi-station apparatus. Station 603 isused for loading and unloading of the substrate wafers. Stations 603-609may have the same or different functions. For example, some of thestations may be devoted to PSAB formation operation, while otherstations may be used for depositing the dielectric diffusion barrierfilm.

In one of the embodiments, individual stations can operate underdistinct process conditions and may be substantially isolated from eachother. For example one station may operate under one temperature regime,while another may operate under a different temperature regime.

In one embodiment, pre-cleaning operation and PSAB layer formationprocess are performed in one preferred temperature regime and arecarried out in one station of the multi-station apparatus. The H₂ plasmapost-treatment and deposition of a dielectric diffusion barrier mayrequire a different temperature regime in some embodiments, and may becarried out in a different station or stations. In other embodiments H₂plasma post-treatment is performed under the same temperature regime asthe PSAB formation and at the same station that performs PSAB formation.In some embodiments, the entire PSAB-forming process includingpre-treatment, passivation, first PSAB layer formation, pinning, and H₂plasma post-treatment is performed in one station of a single station ora multi-station apparatus. In some embodiments, deposition of adielectric diffusion barrier layer may be also performed at the samestation as PSAB layer formation.

In one embodiment example, station 605 may be devoted to pre-clean andto formation of the PSAB layer. Station 605 may operate at a temperaturerange of about 200-300° C., which is preferred in some embodiments forboth PSAB formation and pre-clean operation. H₂ plasma post treatmentcan be carried out at station 607 at a temperature range of about200-400° C. Deposition of dielectric diffusion barrier material, such assilicon carbide, can be carried out in stations 607, 609, and 603 at atemperature range of about 350 to 400° C., which is the preferredprocess temperature according in some silicon carbide depositionprocesses.

Advantageously, pre-clean, passivation, first PSAB layer formation andpinning, may require similar conditions in some embodiments, and can beperformed at one station 605.

According to an embodiment described above, station 605 is a pre-cleanstation and a PSAB formation station. Station 607 serves for H₂ plasmapost-treatment and for deposition of dielectric diffusion barrier layer.Stations 607, 609, and 603 may all serve for deposition of dielectricdiffusion barrier layer. An indexing plate 611 is used to lift thesubstrates off the pedestals and to accurately position the substratesat the next processing station. After the wafer substrate is loaded atstation 603, it is indexed to station 605, where formation of thepre-clean and PSAB layer formation (including all its sub-processesexcept for H₂ post-treatment) is performed. The wafer is then moved tostation 607 where H₂ plasma post-treatment and deposition of diffusionbarrier dielectric is performed. The substrate is further indexed tostation 609, where further deposition of barrier dielectric isperformed, and then indexed to station 603 to deposit more of diffusionbarrier dielectric. The processed wafer is unloaded at station 603, andthe module is charged with a new wafer. During normal operation, aseparate substrate occupies each station and each time the process isrepeated the substrates are moved to new stations. Thus, an apparatushaving four stations 603, 605, 607, and 609 allows simultaneousprocessing of four wafers, wherein at least one station performs aprocess that is different from the processes performed at otherstations. Alternatively, four wafers may be subjected to identicaloperations at all four stations, without dedicating certain stations todeposition of a particular layer.

The process conditions and the process flow itself can be controlled bya controller unit 613 which comprises program instructions for amonitoring, maintaining and/or adjusting certain process variables, suchas HF and LF power, gas flow rates and times, temperature, pressure andthe like. For example, instructions specifying flow rates of silane andammonia for PSAB deposition may be included. The instructions mayspecify all of the parameters to perform operations, according tomethods described above. For example, instructions may includeparameters of pre-clean, passivation, first PSAB layer formation,pinning operations, H₂ plasma treatment, and dielectric diffusionbarrier deposition The controller may comprise different or identicalinstructions for different apparatus stations, thus allowing theapparatus stations to operate either independently or synchronously.

Another example of a multi-station apparatus is illustrated in FIG. 7.The multi-station apparatus 701 includes six stations 703, 705, 707,709, 711, and 713 residing in three separate processing chambers 717,719, and 721, with two stations residing in each chamber. Arobot-containing chamber 715 adjacent chambers 717, 719, and 721provides mechanism for loading and unloading the wafers into thestations. A controller 723 provides instructions for operation of amulti-station apparatus 701. Individual stations within one chamber areisolatable from each other and may carry out identical or differentoperations. In one embodiment, two wafers are simultaneously transferredto stations 703 and 705 residing in one chamber 721 and simultaneouslyundergo identical operations including pre-clean, passivation, firstPSAB layer formation and pinning. After this process is completed, thetwo wafers are removed from the chamber 721, and are simultaneouslyintroduced to stations 707 and 709 residing in chamber 709. In thischamber, a diffusion barrier material layer is simultaneously deposited.The wafers are then removed from chamber 719, and are introduced tostations 711 and 713 residing in chamber 717, where further processingfollows. In some embodiments, formation of PSAB layer may be performedin a multi-chamber apparatus with different PSAB subprocesses performedin different chambers.

There is a variety of ways, in which the PSAB forming process can beimplemented in multi-station tools, such as those shown in FIG. 6 andFIG. 7. In general, the described PSAB process is easily integrated intothe Damascene flow, does not require substantial resource-consuminghandling of substrates, and can be performed in the same apparatus as adielectric diffusion barrier deposition. Further, resistance control viaa passivation operation prior to PSAB layer formation is particularlyadvantageous, since it normally does not require any additionalresources than those normally used for PSAB formation and dielectricdiffusion barrier deposition. Improvement of stress migration parametersis also achieved using the same PECVD platform.

Several embodiments of the described methods will now be illustrated byspecific examples.

EXAMPLES

One example of a PSAB-forming process is illustrated in an experimentaltiming diagram shown in FIG. 8. Flow rates of process gas components andplasma parameters are plotted as a function of time. X-axis listsprocess time in seconds, and Y-axis lists arbitrary parameters thatcorrelate with flow rates and plasma power. Curve (a) corresponds to H₂flow, curve (b) to NH₃ flow, and curve (c) to SiH₄ flow. Curve (d)corresponds to HF RF power level, and curve (e) to LF RF power level.

In the described example; the process is started by a plasma pre-cleanoperation. The partially fabricated semiconductor device having anexposed pattern of copper lines in a dielectric was obtained after a CMPoperation, and was placed into a process chamber of a PECVD VECTOR™apparatus. The entire PSAB-forming process was performed at one stationof a four-station apparatus. First, the substrate was pre-heated to 275°C., and H₂ was introduced into the process chamber at a flow rate of4000 sccm. H₂ was flowed from second 2 to second 28 of the process timeat a pressure of 4 Torr. At second 13, HF RF plasma was ignited and wassustained at a power of 1.23 W/cm² until second 28 of the process time.After the substrate was pre-cleaned with H₂ plasma, H₂ flow and plasmapower were turned off, and NH₃ was introduced into the process chamberto effect the partial passivation of metal surface. NH₃ was flowed fromsecond 28 to second 30 of the process time at a flow rate of 4000 sccmand pressure of 2.3 Torr. After the metal surface has been partiallypassivated, SiH₄ was introduced into the process chamber and was flowedfrom second 30 to second 34 at a flow rate of 120 sccm. NH₃ was flowedconcurrently with SiH₄ at a flow rate of 4000 sccm. The first PSAB layerwas formed at seconds 30-34 of the process, and was subsequently pinned.Pinning occurred at seconds 35-47. During pinning, SiH₄ flow was turnedoff, NH₃ flow was increased to 7000 sccm along with N₂ flow at 2800 sccmand was maintained at this rate at seconds 35-47. Plasma having an HFcomponent at a power level of 0.80 W/cm², and an LF component with powerlevel of 0.37 W/cm² was ignited and was maintained from second 35 tosecond 47. The described processing sequence provided a completedsubstrate with a pinned PSAB layer having a depth of less than about 20Å. The entire PSAB-forming process was performed in a single station ata temperature of 275° C. Subsequently, a Si_(x)C_(y)N_(z) diffusionbarrier layer was deposited on the substrate in a different station ofthe PECVD apparatus at 350° C. using tetramethylsilane, ammonia, andnitrogen as a process gas in a plasma. In another example, aSi_(x)C_(y)O_(c) ODC dielectric diffusion barrier was deposited usingtetramethylsilane and carbon dioxide in a plasma.

The obtained PSAB layer was analyzed using X-ray photoelectronspectroscopy (XPS). This method of analysis provided information on thechemical composition of silicon-containing species in the layer. It wasdetermined that the obtained pinned PSAB layer contained 1.3% of siliconas Cu_(x)Si_(y); 91.4% of silicon as Si_(x)N_(y); and 7.4% of silicon asSiO₂. The interconnect formed using the described above method ofPSAB-layer formation exhibited resistance shift of about 1%.

For comparison purposes, the PSAB layer was formed using an identicalprocedure as described above, but lacking the NH₃ passivating operation.As expected the formed PSAB layer had a greater depth of more than 20 Å.The interconnect with such PSAB layer had a resistance shift of 3%. XPSdata for such PSAB layer provided that silicon in this PSAB layer wasseen as 16.9% Cu_(x)Si_(y), 73% Si_(x)N_(y); and 10.1% as SiO₂.

As it can be seen, partial passivation operation can be used to controlthe resistance of PSAB-containing interconnects, as well as thecomposition, and the thickness of the PSAB layer. Passivation is easilyintegrated into the PSAB process, and does not require additionalequipment or substantial additional time.

Another example illustrates use of hydrocarbon pinning and H₂ plasmatreatment for improvement of via stress migration characteristics. Viastress migration can be quantified by measuring the resistance of astring of connected vias before and after a high temperature annealprocess. The difference in resistance before and after annealcorresponds to a via resistance shift (not to be confused withresistance shift of PSAB-containing and PSAB-free metal lines). In thistest the wafer is subjected to four cycles of thermal anneal between atemperature of 150 and 250° C. for 12 hours. When via resistance shiftexceeds 20%, such via is considered to have unacceptable stressmigration characteristics (bad via). Unacceptable stress migration istypically correlated with formation of voids in a via.

FIG. 9 shows experimental data for the fraction of bad vias on a waferfor the process that does not involve formation of a PSAB layer (a), theprocess involving PSAB formation with hydrocarbon pinning (b), and theprocess involving PSAB formation with H₂ plasma post-treatment. It canbe seen that stress migration parameters are significantly improved inprocesses presented by (b) and (c). PSAB formation with hydrocarbonpinning resulted in less than 3% of bad vias on the wafer, while theprocess with plasma post-treatment resulted in less than 2% of bad vias.

The PSAB process conditions used in the process with hydrocarbon pinning(b) are the following:

Plasma pre-clean: H₂ was flowed at 4000 sccm flow rate; plasma dischargeincluded HF power of 740 W and no LF power. Pre-clean was performed at4.2 torr and 275° C. for 15 seconds.

NH₃ passivation was not used.

Formation of first PSAB layer: SiH₄ was flowed at 120 sccm concurrentlywith NH₃ at 4000 sccm. No plasma was applied. The process was performedat 2.3 ton and 275° C. for 2 seconds

Pinning: cyclopropane was flowed at 500 sccm concurrently with NH₃ at7000 sccm and N₂ at 2800 sccm. Plasma at HF power level of 490 W and LFpower level of 220 W was ignited. The process was performed at 2.3 torrand 275° C. for 12 seconds.

Diffusion barrier deposition: tetramethylsilane was flowed at 1260 sccm,concurrently with NH₃ at 4600 sccm, and N₂ at 3000 sccm. Plasma at HFpower level of 275 W, and LF power level of 241 W was used. The processwas performed at 3.9 torr and at 350° C. Si_(x)C_(y)N_(z) diffusionbarrier layer was formed.

The PSAB process conditions used in the process with H₂ plasmapost-treatment (c) are the following:

H₂ was flowed at 4000 sccm flow rate; plasma discharge included HF powerof 740 W and no LF power. Pre-clean was performed at 4.2 torr and 275°C. for 15 seconds.

NH₃ passivation was not used.

Formation of first PSAB layer: SiH₄ was flowed at 120 sccm concurrentlywith NH₃ at 4000 sccm. No plasma was applied. The process was performedat 2.3 ton and 275° C. for 2 seconds.

Pinning: NH₃ was flowed at 7000 sccm concurrently with N₂ at 2800 sccm.Plasma at HF power level of 490 W and LF power level of 220 W was used.The process was performed at 2.3 ton and 275° C. for 12 seconds.

H₂ plasma post-treatment: H2 was flowed at 9500 sccm. Plasma at HF powerlevel of 200 W and no LF power was used. The process was performed at2.3 ton and 350° C. for 6 seconds.

Diffusion barrier deposition: tetramethylsilane was flowed at 1260 sccm,concurrently with NH₃ at 4600 sccm, and N₂ at 3000 sccm. Plasma at HFpower level of 275 W, and LF power level of 241 W was used. The processwas performed at 3.9 torr and at 350° C.

Although various details have been omitted for clarity's sake, variousdesign alternatives may be implemented. Therefore, the present examplesare to be considered as illustrative and not restrictive, and theinvention is not to be limited to the details given herein, but may bemodified within the scope of the appended claims.

1. A method of forming a protective self aligned buffer (PSAB) layer ofmaterial on or within an exposed metal surface of a partially fabricatedsemiconductor device having a pattern of metal layers in a dielectric,the method comprising: (a) contacting the partially fabricatedsemiconductor device with a PSAB-forming reactant, such that thePSAB-forming reactant reacts with metal atoms of the metal layer andchemically transforms the top portion of the metal layer into a firstPSAB layer, wherein said first PSAB layer resides entirely within saidmetal layer; and (b) subsequently contacting the first PSAB layer with apinning process gas comprising a hydrocarbon in a plasma discharge toform a pinned protective self-aligned buffer layer on or within themetal layer.
 2. The method of claim 1, wherein the metal layer comprisesa metal fill within a damascene region of the partially fabricatedsemiconductor device.
 3. The method of claim 1, wherein the metal layercomprises copper.
 4. The method of claim 1, wherein (a) and (b) areperformed in a PECVD apparatus and (a) is performed without use ofplasma.
 5. The method of claim 1, wherein the first PSAB layer is formedto a depth ranging from about 10 Å to about 1000 Å into the metal layer.6. The method of claim 1, wherein (a) comprises flowing the PSAB formingreactant at a flow rate ranging from about 0.001 sccm to about 10000sccm, wherein (a) is performed at a temperature ranging from about 20°C. to about 500° C., and in a pressure range of between about 10 mTorrto about 100 Torr, and wherein (b) comprises flowing the PSAB formingreactant at a flow rate ranging from about 0.001 sccm to about 10000sccm, wherein (b) is performed at a temperature ranging from about 20°C. to about 500° C., and in a pressure range of between about 10 mTorrto about 100 Torr.
 7. The method of claim 1, wherein the PSAB formingreactant comprises a gas or a vapor selected from the group consistingof SiH₄, GeH₄, PH₃, B₂H₆, AsH₃, CH₄, C_(x)H_(y), H₂S, H₂Se, and H₂Te. 8.The method of claim 1, wherein the first protective self-aligned bufferlayer comprises material selected from the group consisting ofCu_(x)Si_(y), Cu_(x)Ge_(y), Cu_(x)P_(y), Cu_(x)B_(y), Cu_(x)As_(y),Cu_(x)C_(y), Cu_(x)S_(y), Cu_(x)Se_(y), and Cu_(x)Te_(y).
 9. The methodof claim 1, wherein the hydrocarbon used during (b) is selected from agroup consisting of methane, ethane, ethylene, acetylene, propane,propene, propyne, cyclopropane, cyclobutane, butanes, butenes, butynes,and benzene.
 10. The method of claim 1, wherein the pinning process gasfurther comprises a gas or a vapor selected from the group consisting ofN₂, NH₃, H₂, and mixtures thereof.
 11. The method of claim 1, wherein(b) does not comprise depositing material to a thickness of greater than10 Å on the dielectric portions of the partially fabricatedsemiconductor device.
 12. The method of claim 1, further comprisingprior to (a): contacting the partially fabricated semiconductor devicewith a nitrogen-containing reactant, wherein the nitrogen-containingreactant selectively reacts with metal atoms of the metal layer andthereby partially passivates the metal surface to the formation of thefirst PSAB layer.
 13. The method of claim 1, wherein the pinning processgas further comprises a nitrogen-containing gas.
 14. A method of forminga PSAB layer of material on or within an exposed metal surface of apartially fabricated semiconductor device having a pattern of metallayers in a dielectric, the method comprising: (a) contacting thepartially fabricated semiconductor device with a PSAB-forming reactant,such that the PSAB-forming reactant reacts with metal atoms of the metallayer and chemically transforms the top portion of the metal layer intoa first PSAB layer, wherein said first PSAB layer resides entirelywithin said metal layer; (b) subsequently contacting the partiallyfabricated semiconductor device with a pinning reactant in a plasmadischarge to form a pinned PSAB layer on or within the metal layer; and(c) treating the partially fabricated semiconductor device surface withH₂ in a plasma discharge concurrently with (b) or after (b).
 15. Themethod of claim 14, wherein operations (a) comprises flowing a processgas comprising the PSAB-forming reactant at a flow rate ranging fromabout 0.001 sccm to about 10000 sccm, wherein (a) is performed at atemperature ranging from about 20° C. to about 500° C., and in apressure range of between about 10 mTorr to about 100 Torr and whereinoperation (b) comprises flowing a process gas comprising the pinningreactant at a flow rate ranging from about 0.001 sccm to about 10000sccm, wherein (b) is performed at a temperature ranging from about 20°C. to about 500° C., and in a pressure range of between about 10 mTorrto about 100 Torr.
 16. The method of claim 14, wherein operations (b)and (c) are performed concurrently, and the pinning reactant is selectedfrom the group consisting of N₂, NH₃, a hydrocarbon, a gas from thefamily of methyl-substituted silanes, a gas from the family ofmethyl-substituted amines hexamethyldisilazane (HMDS), and mixturesthereof.
 17. The method of claim 14, wherein (b) and (c) are performedconcurrently and comprises contacting the partially fabricatedsemiconductor device having the first PSAB layer with a process gascomprising H₂ and a pinning reactant selected from the group consistingof NH₃, N₂ and mixtures thereof, in a plasma discharge.
 18. The methodof claim 14, wherein (c) is performed subsequent to (b) and the pinningreactant is selected from the group consisting of N₂, NH₃, ahydrocarbon, a gas from the family of methyl-substituted silanes, a gasfrom the family of methyl-substituted amines hexamethyldisilazane(HMDS), and mixtures thereof.
 19. The method of claim 14, furthercomprising prior to (a): contacting the partially fabricatedsemiconductor device with a nitrogen-containing reactant, wherein thenitrogen-containing reactant selectively reacts with metal atoms of themetal layer and thereby partially passivates the metal surface to theformation of the first PSAB layer.